Electronic supplementary information (ESI) Tetradentate selenium ligand as a building block for homodinuclear complexes of Pd(II) and Ru(II) having seven membered rings or bis-pincer coordination mode: high catalytic activity of Pd-complexes for Heck reaction Dipanwita Das, Pradhumn Singh, Monika Singh‡ and Ajai K. Singh* Department of Chemistry, Indian Institute of Technology, Delhi, New Delhi110016, India

Table S1. Crystal data and structural refinements for L, 1, 2 and 3

L (763938) 1 (765901) 2 (763939) 3 (770943) Empirical formula

C34H30Se4 C40H40Cl2O8Pd2Se4 C44H38B2F8N2Pd2Se4 C46H42Cl2F12P2Ru2Se4

Crystal size [mm]

0.504 × 0.314 × 0.144

0.203 × 0.150 × 0.065

0.524 × 0.342 × 0.178

0.524× 0.324 × 0.184

θ range [°] 2.35 – 28.32 2.25 – 25.05 2.25 – 25.73 2.20 – 28.32 Index ranges −14 ≤ h ≤ 14

−12≤ k ≤ 12 −13 ≤ l ≤ 13

−13≤ h ≤ 13 −17≤ k ≤ 17 −18≤ l ≤ 18

−26≤ h ≤ 26 −12≤ k ≤ 12 −22≤ l ≤ 22

−34≤ h ≤ 34 −13≤ k ≤ 13 −22≤ l ≤ 22

Max./min. Transmission

0.489/ 0.164 0.771/ 0.482 0.493/ 0.207 0.545/ 0.282

Data/restraints/ parameters

2596 / 0 / 172 8180 / 40 / 494 4042 / 1 / 280 4996 / 12/ 296

Final R indices [ I >2σ(I)]

R1 = 0.0997, wR2 = 0.1692

R1 = 0.0610, wR2 = 0.1391

R1 = 0.0458, wR2 =0.1323

R1 = 0.0836, wR2 = 0.1650

R indices (all data)

R1 = 0.1141, wR2 =0.1745

R1 = 0.1071, wR2 = 0.1579

R1 = 0.0572, wR2 =0.1397

R1 = 0.1493, wR2 = 0.1923

Largest diff. peak/hole [е.Å-3]

0.891/ -0.861 1.209 / -0.668 1.220 / -0.676 0.848/ -0.682

Table S2. Bond Lengths and Bond Angles of L, 1, 2 and 3 Bond Length [Ǻ] Bond Angle [°]

L

Se(1)—C(5) 1.907(9) Se(1)—C(4) 1.971(9) Se(2)—C(12) 1.939(8) Se(2)—C(11) 1.973(10)

C(5)– Se(1)–C(4) 103.5(4) C(12)–Se(2)–C(11) 98.6(4) C(3)–C(4)–Se(1) 104.2(6) C(6)–C(5)–Se(1) 124.5(7) C(10)–C(5)–Se(1) 116.2(7) C(2)–C(11)–Se(2) 112.1(7) C(17)–C(12)–Se(2) 121.7(7) C(13)–C(12)–Se(2) 117.0(7)

1

Pd(1)—C(2) 2.128(13) Pd(1)—C(3) 2.143(11) Pd(1)—C(1) 2.160(11) Pd(1)—Se(2) 2.4494(16) Pd(1)—Se(1) 2.4557(17) Se(1)—C(10) 1.943(10) Se(1)—C(4) 2.022(11) Se(2)—C(15) 1.922(10) Se(2)—C(14) 1.994(10)

C(2)–Pd(1)–C(3) 37.5(5) C(2)–Pd(1)–C(1) 37.1(5) C(3)–Pd(1)–C(1) 66.8(5) C(2)–Pd(1)–Se(2) 125.9(4) C(3)–Pd(1)–Se(2) 158.1(4) C(1)–Pd(1)–Se(2) 92.4(4) C(2)–Pd(1)–Se(1) 127.9(4) C(3)–Pd(1)–Se(1) 94.3(4) C(1)–Pd(1)–Se(1) 160.1(4) Se(2)–Pd(1)–Se(1) 105.54(5) C(10)–Se(1)–C(4) 92.3(5) C(10)–Se(1)–Pd(1) 111.5(3) C(4)–Se(1)–Pd(1) 102.3(3) C(15)–Se(2)–C(14) 97.7(4) C(15)–Se(2)–Pd(1) 104.2(3) C(14)–Se(2)–Pd(1) 109.0(3)

2

Pd(1)—C(9) 2.009(5) Pd(1)—N(1) 2.148(5) Pd(1)—Se(2) 2.4005(8) Pd(1)—Se(1) 2.4084(7) Se(1)—C(6) 1.942(6) Se(1)—C(7) 1.950(6) Se(2)—C(12) 1.931(7) Se(2)—C(11) 1.954(6)

C(9)–Pd(1)–N(1) 178.0(2) C(9)–Pd(1)–Se(2) 86.09(15) N(1)–Pd(1)–Se(2) 92.18(13) C(9)–Pd(1)–Se(1) 85.97(15) N(1)–Pd(1)–Se(1) 95.75(13) Se(2)–Pd(1)–Se(1) 172.06(3) C(6)–Se(1)–C(7) 100.8(3) C(6)–Se(1)–Pd(1) 102.22(17) C(7)–Se(1)–Pd(1) 93.79(17) C(12)–Se(2)–C(11) 98.7(3) C(12)–Se(2)–Pd(1) 105.0(2) C(11)–Se(2)–Pd(1) 93.93(17)

3

Ru(1)—C(23) 2.139(15) Ru(1)—C(22) 2.176(16) Ru(1)—C(21) 2.177(19) Ru(1)—C(19) 2.19(2) Ru(1)—C(18) 2.20(2) Ru(1)—C(20) 2.215(16) Ru(1)—Cl(1) 2.394(4) Ru(1)—Se(1) 2.4945(18) Ru(1)—Se(2) 2.5164(18) Se(1)—C(1) 1.923(11) Se(1)—C(7) 1.966(13) Se(2)—C(12) 1.918(13) Se(2)—C(11) 1.985(12)

C(23)–Ru(1)–Cl(1) 130.2(9) C(22)–Ru(1)–Cl(1) 163.6(5) C(21)–Ru(1)–Cl(1) 139.6(7) C(19)–Ru(1)–Cl(1) 89.2(7) C(18)–Ru(1)–Cl(1) 95.1(11) C(20)–Ru(1)–Cl(1) 104.9(7) C(23)–Ru(1)–Se(1) 85.9(5) C(22)–Ru(1)–Se(1) 100.0(5) C(21)–Ru(1)–Se(1) 135.1(7) C(19)–Ru(1)–Se(1) 134.1(11) C(18)–Ru(1)–Se(1) 100.6(11) C(20)–Ru(1)–Se(1) 163.0(5) Cl(1)–Ru(1)–Se(1) 85.23(9) C(23)–Ru(1)–Se(2) 138.3(9) C(22)–Ru(1)–Se(2) 104.5(5) C(21)–Ru(1)–Se(2) 86.8(5) C(19)–Ru(1)–Se(2) 134.0(12) C(18)–Ru(1)–Se(2) 166.7(8) C(20)–Ru(1)–Se(2) 101.5(7) Cl(1)–Ru(1)–Se(2) 90.81(9) Se(1)–Ru(1)–Se(2) 91.74(5) C(1)–Se(1)–C(7) 98.2(5) C(12)–Se(2)–C(11) 101.9(6) C(12)–Se(2)–Ru(1) 102.4(4) C(11)–Se(2)–Ru(1) 109.9(3)

IR Data

L (KBr, cm−1): 3012(νC—H(aromatic)), 2908(νC—H(aliphatic)), 1564(νC=C(aromatic)), 733(νC—

H(aromatic bend)).

1 (KBr, cm−1): 3032(νC—H(aromatic)), 2896(νCH(aliphatic)), 1589 (νC=C(aromatic)), 1089 and

630 (νCl—O ), 733( νC—H(aromatic bend))

2 (KBr, cm−1): (KBr, cm−1): 3046(νC—H(aromatic)), 2873(νC—H(aliphatic)), 1604−

1467(νC=C(aromatic) and νC=N(aromatic) ), 734(νC—H(aromatic bend)).

3 (KBr, cm−1): 3213(νC—H(aromatic)), 2842(νC—H(aliphatic)), 1534(νC=C(aromatic)), 845(νP—

F(aromatic bend)), 730(νC—H(aromatic bend)).

Fig S1. C–H···π and π···π interactions in L

Fig S2. In 1 3-D network formation as a result of weak O···H interactions; 2.384(15) – 2.968(18) Å

Fig S3. BF4¯ participating in intra- and inter-molecular H···F interactions in 2; 2.390(7)- 2.922(23) Å

Fig S4. Two cationic units [Pd2(Py)2(L)]2+ linked by BF4¯ through H···F interactions

Fig S5. Complex 3-D network formation in 3 as a result of weak H···F and H···Cl interactions H···F length range 2.649(16) – 3.051(18) Å, H···Cl length range 2.703(4) – 3.025(3) Å

Fig S6. 77Se{1H} NMR of L

Fig S7. 77Se{1H} NMR of 1

Fig S8. 77Se{1H} NMR of 2

Fig S9. 77Se{1H} NMR of 3